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Abstract

Translated from Chinese

一种用于合成星型杂臂橡胶的方法属于橡胶合成领域。 A method of synthesizing a star belonging miktoarm rubber synthetic rubber art.目前，轮胎的制备基本上三胶并用，即天然橡胶、丁苯橡胶和丁二烯橡胶的共混，三胶并用采取的是机械共混的方法，共混存在胶种间的相容性不好，从而影响了各种助剂的分散、橡胶的硫化及硫化胶的性能。 At present, the manufacture of tires and rubber with substantially three, i.e., natural rubber, styrene-butadiene rubber and butadiene rubber blend, taken with three glue and mechanical blending method, there is no compatibility among types of plastic blend good, thus affecting the dispersion properties of the vulcanized rubber and vulcanized rubber of various adjuvants.本发明通过不同的结构调节剂、不同的单体比例合成了不同组成结构的杂臂聚合物。 The present invention by various structure modulating agent, the ratio of different monomers arm polymer synthesized structures of different compositions.本发明产品有较好的耐寒性和耐磨性，较好的抗湿滑性，证明该胶有较小的滚动阻力。 The present invention product has good abrasion resistance and cold resistance, good wet skid resistance, show that the glue has a smaller rolling resistance.该方法简单易行，容易操作。 The method is simple, easy to operate.

Description

Translated from Chinese

一种用于合成星型杂臂橡胶的方法 A method for synthesizing star-shaped rubber miktoarm

技术领域 FIELD

本发明涉及高分子化合物合成领域，特别涉及橡胶合成领域。 The present invention relates to the synthesis of a polymer compound, and more particularly relates to the field of synthetic rubber.背景技术 Background technique

当前能源和环境问题是人类面临的两大重要问题。 The current energy and environmental issues are two major problems facing humanity.在橡胶行业，降低汽车轮胎的滚动阻力成为重要的性能要求。 In the rubber industry, reduce car tire rolling resistance has become an important performance requirements.随着汽车工业的迅猛发展，对轮胎许多其它重要性能的要求也更高、更全面，如抗湿滑性(安全性)、耐磨性(耐用性)等。 With the rapid development of automobile industry, the requirements of many other important properties of the tire is also higher, more comprehensive, such as wet skid resistance (safety), abrasion resistance (durability) and so on.研究表明以往各种通用胎面胶的各性能间存在着明显的矛盾。 Previous studies have shown that among the various general performance tread compound there is a clear contradiction.滚动阻力小、耐磨性好的橡胶，则抗湿滑性差，反之亦然。 Rolling resistance, good wear resistance rubber, the wet skid resistance is poor, and vice versa.人们在研究中发现， People in the study found,

通过各种具有不同Tg的胶料的共混确实可以达到各种性能的平衡。 By having different Tg various blends of rubber compounds can indeed achieve the balance of properties.目前，轮胎的制备基本上三胶并用，即天然橡胶、丁苯橡胶和丁二烯橡胶的共混，三胶并用采取的是机械共混的方法，共混存在胶种间的相容性不好，从而影响了各种助剂的分散、橡胶的硫化及硫化胶的性能。 At present, the manufacture of tires and rubber with substantially three, i.e., natural rubber, styrene-butadiene rubber and butadiene rubber blend, taken with three glue and mechanical blending method, there is no compatibility among types of plastic blend good, thus affecting the dispersion properties of the vulcanized rubber and vulcanized rubber of various adjuvants.

解决这种矛盾的途径是研制新型聚合物，即合成既改善滚动阻力又不损害抗湿滑性的橡胶。 Way to resolve this contradiction is to develop new polymers that synthesis of both to improve the rolling resistance without compromising wet skid resistance rubber.正是这个原因，德国的KHNordsiek等人经过研究于1984年提出了集成橡胶的概念。 For this reason, the German KHNordsiek, who put forward the concept through research integrated rubber in 1984.集成橡胶的理念是由不同聚合物分子链段提供不同的性能，最终使橡胶具有最全面的性能。 Concept of integral rubber different properties to provide different polymer chain segments, the most comprehensive final rubber properties.德国的Hiils公司于1984年通过苯乙烯、丁二烯、异戊二烯的负离子三元共聚首先成功地合成了SIBR，商品名为Vestogral，而美国的Goodyear公司也相继开发出了同类产品。 Germany Hiils in 1984 by styrene, butadiene, isoprene terpolymer negative first successful synthesis of SIBR, trade name Vestogral, Goodyear and the US companies have also developed a similar product.这种化学合成的集成橡胶由于将不同的链段键合于一条高分子链上，从而限制了不同链段的自由运动，使混合更为均匀和彻底，硫化和硫化胶的性能更为优越。 Such chemical synthetic rubber since the integration of the different segments bonded to the polymer chain one, thereby limiting the freedom of movement of the various segments, more uniform and thorough mixing, vulcanization and vulcanizate properties superior.

3U.S.Pat.No.4,843,120中描述的是合成含有多个玻璃化转变温度的橡胶， 在-110°C〜-20°C会显示出一个玻璃化温度，在-50°C〜0°C会出现另一个玻璃化温度。 3U.S.Pat.No.4,843,120 described in the synthetic rubber comprising a plurality of glass transition temperatures, exhibits a glass transition temperature of -110 ° C~-20 ° C will, at -50 ° C~0 ° another C glass transition temperature occurs.具体方法是分两釜串联，单体按一定的配比连续进入第一釜，当达到一定的转化率后进入第二釜，在第二釜中偶联。 The specific method is divided into two reactor series, according to a certain ratio of the monomer continuously into the first tank, when a certain rate of conversion into the second tank, the second tank in the coupling.各釜聚合条件不同，加入的调节剂也不同。 Different polymerization conditions in each reactor, the addition of different modifiers.此法的特点是在不同的转化阶段加入调节剂、偶联剂，合成不同分子链段结构、分子量分布变宽的聚合物。 Advantage of this method is added at different stages of conversion modifiers, coupling agents, different synthetic molecular chain structure, polymer broadened molecular weight distribution.但是第一釜中的转化率、 聚合温度难以控制，活性种末端的空间位阻大则难于偶联、聚合至后期由于胶液的粘度变大难于偶联、聚合温度和偶联剂的加入方式等亦会影响偶联效率，还会较大地影响所得聚合物的特性粘度，故对冷流和加工性能有较大的影响。 However, the conversion of the first tank, the polymerization temperature is difficult to control, large steric hindrance is difficult to end the active species conjugated, was added to the polymerization glue embodiment late increases the viscosity of the coupling is difficult, and the polymerization temperature of the coupling agent and the like also affect the coupling efficiency, but also greatly influence the intrinsic viscosity of the resulting polymer, and therefore have a greater influence on the processability and the cold flow.

发明内容 SUMMARY

本发明的目的是用一种较为简便的合成方法，设计合成一种杂臂星型橡胶。 Object of the present invention is to use a more simple method of synthesis, the synthesis of a hybrid design arm star rubber.该聚合物物在结构上为星型，且同一聚合物分子上含有不同组成的臂(如， 聚异戊二烯臂，丁苯共聚物臂)，故称之为杂臂。 The polymer was a star, and contains the same structure in the polymer molecules of different compositions of arms (e.g., polyisoprene, styrene-butadiene copolymer arms), so called hybrid arm.它在组成结构上不同于上述文献中各臂组成均相同的对称性的偶联聚合物，即星型聚合物各臂都相同(均为丁苯臂或均为异戊二烯一苯乙烯一丁二烯无规分布的聚合臂)。 It differs from the above documents are the same as each arm consisting of a polymer conjugate symmetry in composition, i.e., each arm star polymer are the same (both are isoprene or styrene-butadiene-styrene arm a polymeric arms butadiene random distribution).正是由于杂臂的存在，使其相当于将聚异戊二烯橡胶和不同微观结构的丁苯橡胶链合到同一分子链上，实现聚合物在分子结构上的共混，改善橡胶及其硫化的性能， 抗湿滑性能优，滚动阻力低，综合性能优异的胶种。 Because of the presence of heteroatoms arm, it corresponds to the styrene-butadiene rubber and polyisoprene chains of different microstructures bonded to the same molecular chain, and a polymer blend in the molecular structure, and improve rubber sulfurized performance, excellent wet skid resistance, low rolling resistance, excellent performance plastic types.此外，该合成方法操作简便，单釜即可，无需采用双釜，既简化了操作又节约了生产成本。 In addition, the synthesis method is simple, one-pot without the need of double autoclave, simplifies operation and saving production costs.

本发明的效果：本发明通过不同的结构调节剂、不同的单体比例合成了不同组成结构的杂臂聚合物。 Effect of the Invention: The present invention by various structure modulating agent, the ratio of different monomers arm polymer synthesized structures of different compositions.经DSC测试证明该聚合物在-IO(TC〜-5(TC存在一个玻璃化转变温度，在-5(TC〜2(TC存在另一玻璃化转变温度；或者在-70 。C〜20。C间存在一较宽的玻璃化转变区。经DMTA测试该聚合物在-IO(TC〜-60 。C范围内有较大的tg6值，证明该胶有较好的耐寒性和耐磨性；在0°C〜20 。C范围内有较大的tgS值，证明该胶有较好的抗湿滑性；在6(TC〜8(TC内有较低的tg6值，证明该胶有较小的滚动阻力。在表II中列出了该胶与USPat.No.5,272,220中胶样的机械性能及动态力学性能的对比。 DSC of the polymer was tested in -IO (TC~-5 (TC presence of a glass transition temperature in the -5 (TC~2 (TC there is another glass transition temperature; or -70 .C~20. there is a wide transition area between the glass C. the polymer was tested in a DMTA -IO (tg6 a larger value within a range TC~-60 .C prove that the adhesive has good cold resistance and abrasion resistance ; there in the range of 0 ° C~20 .C tgS larger value, prove that the adhesive has good wet skid resistance; in 6 (TC~8 (tg6 has a lower value within the TC, the adhesive has proved smaller rolling resistance. lists the mechanical properties and comparison of the dynamic mechanical properties of the gel-like gum USPat.No.5,272,220 in table II.

附图说明 BRIEF DESCRIPTION

图l偶联前聚异戊二烯GPC谱图图2最终产物的GPC谱图图3聚合物核磁谱图 FIG. L 2 before the final product of the coupling of FIG GPC chart of polyisoprene GPC chart in FIG. 3 NMR spectrum of polymer

图4有两个玻璃化转变温度的聚合物的DSC谱图图5聚合物的DMTA曲线 FIG 4 FIG polymer has a DSC spectrum of two glass transition temperatures of the polymers DMTA curve 5

10聚合结束后用乙醇终止反应，加入聚合物重量0.5%的防老剂，除去溶剂后放入5CTC真空烘箱中烘干。 After termination of the reaction with ethanol and 10 the polymerization, 0.5% by weight antioxidant polymer, solvent was removed in vacuo into 5CTC drying oven.

由GPC测定聚合物的数均分子量为210， 000;分子量分布1.4;聚合物平均臂数为4臂。 Determined by GPC number average molecular weight of 210, 000; molecular weight distribution of 1.4; the average number of polymer arms 4 arms.由丽R测定聚合物中聚异戊二烯臂上约92%的异戊二烯结构单元为l， 4结构，约8%的为3, 4结构；丁苯臂上50%的聚丁二烯结构单元为乙烯基结构，50%为1， 4结构。 Li R polyisoprene polymer was measured by the arms about 92% isoprene structural unit L, the structure 4, about 3 to 8%, the structure 4; 50% of the styrene-butadiene arms polybutadiene alkenyl structural unit a vinyl structure, 50% of 1, 4 structure.聚合物在-80°C〜-40。 Polymer -80 ° C~-40.C存在一较宽的玻璃化转变温度区。 There is a wider region of the glass transition temperature C.

由图1和图2可以看出偶联前的GPC为单峰分布，而偶联并加入第二歩料反应后分子量呈双峰分布，数均分子量变大，分子量分布变宽，由上图可以看出偶联效果明显，偶联效率都达到80%以上，偶联度基本为3〜5。 FIG 1 and FIG 2 can be seen that the front coupling GPC unimodal distribution, and the coupling reaction was added after the second feed ho bimodal molecular weight distribution, a number-average molecular weight becomes large, the molecular weight distribution broadens from the FIG. It can be seen clearly the effect of coupling, the coupling efficiency is 80% or more, the degree of coupling is substantially 3 to 5.从图2中我们还可以看到有一部分较大分子量的聚合物生成，这主要可能是由于二乙烯基苯在偶联过程中发生交联，生成多臂聚合物。 From Figure 2 we can also see a portion of higher molecular weight polymer formation, which may be due mainly divinylbenzene crosslinking occurs during coupling to produce multi-arm polymer.由此可知，用此方法可以有效地合成杂臂型的聚合物。 This indicates that this method can be effectively synthesized hetero-armed polymer.

由图3可以看出，所得聚合物确实含有异戊二烯、丁二烯、苯乙烯单元; As can be seen from Figure 3, the resulting polymer does contain isoprene, butadiene, styrene unit;

由图4可以看出，所得聚合物由两个玻璃化转变^^度，证明该聚合物存在两相，聚合物确实存在杂臂。 As can be seen from Figure 4, the resulting polymer consists of two glass transition ^^ degree, to prove the existence of the two-phase polymer, the polymer does exist heteroaryl arm.

由图5可以看出，TgS峰为一平滑的宽峰，证明聚合物分子链的变化使各相得到较好的相容性。 As can be seen from Figure 5, TgS peak is a broad peak smooth, demonstrated changes in the polymer molecular chain of each phase to obtain good compatibility.在0X:有较高的TgS值，说明具有较高的抗湿滑性能；而在6(TC时有较低的Tg5值，证明有较低的滚动阻力。 In 0X: TgS a higher value, indicating with high wet skid resistance; in 6 (Tg5 have lower TC values, the prover has a lower rolling resistance.

(2)由上图可以看出，本发明产品在0'C时有较高的TgS值，说明具有较高的抗湿滑性能；而在6(TC时有较低的Tg 5值，证明有较低的滚动阻力。 (2) can be seen from the figure, the present invention has a higher product value TgS at 0'C, description has high wet skid resistance; in 6 (a lower value of Tg 5 TC, the prover have lower rolling resistance.

Claims (3)

Translated from Chinese

1、一种用于合成星型杂臂橡胶的方法，其特征在于，包括以下步骤：1)聚合：配制含有四氢呋喃的异戊二烯溶液，溶剂为环己烷、正己烷、或由这两种化合物组成的混合溶剂，异戊二烯单体的浓度为10～20克单体/100毫升溶剂；将上述异戊二烯溶液压入反应釜后加入有机锂引发聚合，聚合温度在50℃～90℃之间，聚合时间1～2小时；有机锂用量为0. 6～2毫摩尔每100克异戊二烯单体；四氢呋喃与有机锂的摩尔比例在0.5～10；2)加入偶联剂二乙烯基苯偶联0.5～1.5小时，偶联剂二乙烯基苯与有机锂比例在0.2～1.2之间；3)加入含有丁二烯、苯乙烯混合物以及调节剂的混合溶液聚合；调节剂为四氢呋喃、二氧六环、二缩乙二醇二甲醚、乙二醇二甲醚、四甲基乙烯基二铵、五甲基二乙烯基三胺以及烷基苯磺酸盐类，其用量与有机锂的摩尔比例在1～40之间；其中丁二烯占 1. A method for synthesizing a star miktoarm rubber, characterized by comprising the following steps: 1) Polymerization: formulating a solution containing tetrahydrofuran isoprene, the solvent is cyclohexane, n-hexane, or by the two a mixed solvent composed of compounds, the concentration of the isoprene monomer is 10 to 20 grams of the monomer / solvent 100 ml; later, the isoprene solution was pressed into the autoclave to initiate the polymerization is added an organolithium polymerization temperature at 50 deg.] C ~ between 90 ℃, the polymerization time is 1 to 2 hours; the amount of the organic lithium 0.6 to 2 millimoles per 100 grams of isoprene monomer; molar ratio of tetrahydrofuran to organolithium of from 0.5 to 10; 2) adding a coupling coupling with divinylbenzene 0.5 to 1.5 hours, a coupling agent divinylbenzene with an organolithium ratio between 0.2 and 1.2; 3) solution containing butadiene, styrene, a mixed solution and the adjustment of the polymerization mixture; modifiers is tetrahydrofuran, dioxane, dipropylene glycol dimethyl ether, ethylene glycol dimethyl ether, tetraethylene diammonium methylvinyl, pentamethyl diethylenetriamine alkylbenzene sulfonates a molar ratio of an amount of organolithium between 1 to 40; wherein the butadiene represented丁二烯、苯乙烯混合物质量的50％—90％，异戊二烯和丁二烯、苯乙烯混合物的质量比为0.43～2.33；聚合温度在50℃～90℃之间，聚合时间1～2小时；4)聚合结束后用乙醇终止反应，加入聚合物重量0.5％～1％的防老剂，除去溶剂后烘干。 Butadiene, styrene, a mixture of 50% to 90% by mass of isoprene and butadiene, styrene mass ratio of the mixture is 0.43 to 2.33; the polymerization temperature is between 50 ℃ ~ 90 ℃, polymerization time 1 2 hours; 4) after completion of the polymerization reaction was quenched with ethanol, 0.5% to 1% by weight antioxidant polymer after drying to remove the solvent.